Smelting copper-lead drosses and the like



Patented M... 7, 1944 ,SMELTING COPPER-LEAD naossus AND Edward P. Fleming, Los Angeles, Calii., and Don-. aid H. McIntosh, Corpus Christi, Tex assignors .to American Smelting and Refining Company, New York, N. Y., a corporation of NewJersey' No Drawing. Application August 21, 1943,

Serial No. 499,550 I I 12 Claims.

This invention relates to the metallurgical processes and more particularly to smelting of .drosses, mattes, and the like, containing substantial quantities of copper and lead.

This application is a. continuation-impart-'of our co-pending application Serial No. 449,662, filed July K1942.

In the processes normally practiced in the recovery of lead and copper from ores containing these metals, there is produced a copper-lead dross. This dross as ageneral rule will contain magnetic oxide of, iron which may vary in amounts from 2 to 5 per cent by weight, which makes it refractory to smelt by known processes. It has heretofore been standard practice to remove this iron as a silicate slag by adding sillceous ores and scrap iron and smelting in a reverberatory furnace operated at a temperature between 1300 and 1400 C. Maintalningthis relatively high temperature results in high fuel consumption, a copper speiss or matte of relatively low copper to lead ratio, a slag high in lead and copper that must be retreated in a lead blast furnace, and a lead bullion fromthe reverberatory containing substantial cjuantitiesof copper, veryfrequently of theorder .of two and 'a half per cent. s

It will be apparent that such practice entails a large circulating load of copper, making increased tonnage of copper-lead dross to be resmelted although one of, the importa'iflt purposes -In accordance with the present invention, the undesirable drawbacks of the foregoing practice are minimized or eliminated in that copper-lead dross may be treated in the reverberatory furnace to produce lead which has a very low copper content and at the same time a copper speiss" with a high copper to leadratio.

Accordingto the invention,a flux may be provided'which on mixture with the dross to be 'smelted permits of treatment in the reverberatory furnace at a temperature of 800-1000 (3., resulting in a lower fuel consumption than is required in the standard processes heretofore practiced wherein the operating temperatures are considerably higher. after described in more detail, when mixed with copper-lead dross and the charge smelted, will cause a sodium sulphide slag I (probably better termed .a sodium sulphide-matte) to beformed in, which the iron such as magnetic oxide of iron or iron sulphide and other refractory substances,

in, the smelting operations is the separation of the copper and lead sofas to produce bulli'on as free from copper as possible and a copper matte or speiss product as free from leadas possible. But the prior standard commercial practice has fallen far short in attaining'the most desirable goal. In fact, the method heretofore constituting standard practice results inthe production of a copper product with a low copper to'lead ratio; whereas it is of great'economical advantage to produce a copper product of high copper to lead ratio because very frequently this product must be shipped from the lead smelter to copper plants which may be at greaterror less distances away.

The shipment of the copper product'containing large quantities of lead entails high freight costs and high treatment costs-at the copper plant 3 per ton of copper, and a large loss of lead at the copper plant.

The lead recovered in the copper plant will be obtained usually in the form of fume which must be converted to bullion, so it is usually returned tothe lead smelter with consequent further losses and. costs of treatment of the fume to convert it to bullion.

such as smalllamounts of silica, will collect. The

(matte, which may be currently drawn'ofl, will .contain practically all of the iron and sulphur 3 contained in thedross and generally will itself have a good enough copper-lead ratio to allow of shipment direct to the copper smelter. The copper. speiss product will have a copper to lead ratio of the order of 5 or 6 ml andin many instances a higher ratio, The lead bullion-from the reverber'atory may be causedto have a copper content of less than one per cent.

Although the novel features which are believed to be characteristic of this invention will be particularly pointed out in the claims appended hereto, the invention itself, as to its objects and advantages, and the manner in which-it may be carried out, may be better understood by referring to the following description in which certain specific disclosures 'are madefor purpose of explanation. It will be understood, however, that the processes and the steps thereof may be modified in various respects without departing from the broader aspects of v the invention.

In one manner of practicing the. invention, one hundred andforty-four tons of copperlead dross were intimately mixedwith a flux containing sodium carbonate, coke. and litharge and treated in the reverber-atory at 'a, working temperature of abo'ut900" C. {The dross to be treated contained 62% Pb, 18% Cu,.7.8% 'As, 3.2% Sb. Seven tons of sodium carbonate, two tons of coke and three and seven-tenths tons of litharge slag were used as the mix. The-lithargeslag contained Pb,

Moreover, certain fluxes herein 1.0% Cu, .05% As and .05% Sb and was produced by smelting baghouse dust.

The amounts and assays of the products resulting from the treatment of the foregoing charge were as follows: Forty-three and one-tenth tons of speiss,'containing 11% Pb, 57% Cu, As. 6.6% Sb; eight and eight-tenths tons of slag (better termed "matte"), containing 0.5% Pb, 15% Cu, 0.5% As, 0.2% Sb, 10% S, 16% Fe; eighty-five tons of bullion, containing 96.5% Pb, 0.94% Cu, 0.52% As, 1.86% Sb.

It will be observed that the bullion produced contained less than 1% Cu; The soda matte had a copper to lead ratio of 30 to 1 and the speiss, a copper to lead ratio of better than 5 to 1; ,whereas in accordance with standard procedure heretofore practiced of treating a like dross in-the reverberatory using siliceous ores and scrap iron as fiuxing agents and operating at temperatures of 1300-1400 C., it was not uncommon to produce speiss and matte having a copper to lead ratio of 2 to 2.5 to 1 and a lead bullion containing upwards of 4% copper.

It will be apparent from the foregoing that the treatment of copper-lead dross in accordance with this invention has the advantage of lower fuel consumption, because of the lower working temperature; less copper is retained in the bullion; and less lead is retained in the speiss.

If desired, certain other compounds of sodium may be used in combination with, or in place of, sodium carbonate in the flux and, of course, other known carbonaceous reducing agents may be used in combination with, or in place of, coke. For example, we have, in some instances on a smaller scale, used sodium sulphate in place of sodium carbonate although up to the present our preference has been to use the latter. In one instance a copper lead dross containing 62.2% Pb,

\ 17.6% Cu, 1% Fe, 2.4% As, 6.4% Sb, 1.2% S was intimately mixed with a flux as follows: 3% of lead oxide by weight of dross, 3% of fine coke by weight of dross, 6% of sodium sulphate by weight of dross. Upon smelting treatment this produced a speiss which assayed 51.6% Cu, 8.4% Pb, or,a ratio of copperto lead of better than 6 to 1; and a soda matte which assayed 35.6% Cu; 5.4% Pb, or a ratio of better than 6.5 to 1. i

In another instance the same dross was treated with a flux made up of 3%. of litharge by weight of dross, 5% of fine coke by weight of dross, 6% of sodium sulphate by weight of dross, which yielded a speiss which assayed 53.3% Cu, 7% Pb, or a copper to lead ratio of about 8 to 1; and a soda matte which assayed 34.5% Cu, 5.1% Pb or a copper to lead ratio of about 6.8 to 1.

In another instance a dross which analyzed 50.0% ,Pb, 24.9% Cu, 7.5% As, 1.6% Sb and 1.5% S was treated with a flux made up of 5% sodium sulphate, 3% fine coke, 3% litharge slag. This resulted in a spelss containing 9.4% Pb, 60.4% Cu, 19.6% As, 3% Sb, 0.6% S, or a copper to lead ratio of about 6.4 to 1; a soda matte containing 5.8% Pb, 25.0% Cu, 1.0% As, 0.2% Sb, 17.2% S, or a copper to lead ratio of about 4.3 to 1'.

Ordinarily it will require a higher percentage of sodium sulphate than sodium carbonate if the former is used in the flux instead of the latter and also a higher percentage of coke. But it may be noted that by the use of the former additional sulphur is added to the dross charge'which has the advantage of providing more sulphur available to react with any magnetite in the charge to form FeS and also to form a sodium sulphide matte in which the iron more readily collects. Fu thermore, the formation of the FeS and sodium sulphide matte reduces difficulties likely to arise from the formation of accretions in the furnace if the iron is in the form of magnetite.

In addition to the use of sodium carbonate or sodium sulphate in the flux, the invention contemplates the use of other sodium compounds, such as sodium sulphide and the like, which in the smelting operation will form a sodium sulphide matte effective to hold in solution any iron compounds present. It will be understood, of course, that as to the selection of the fluxing agents for use in commercial practice, consideration normally will be given to the matter of costs in relation to results.

Generally speaking, copper-lead drosses may be encountered in commercial practice which will assay 18% to Cu, to Pb and will contain varying amounts of As, Sb, S and Fe. If the antimony in the dross is low, the copper speiss produced by using flux in accordance with the invention will approximate a true copper arsenide with some lead in solution. If an appreciable amount of antimony is in the dross, copper speiss wil1 consist substantiall of a mixture of copper arsenide and copper antimonide when treated according to the invention. But in any case, the Fe and S in the speiss will be very low as these elements may be slagged off. A typical analysisof some of the soda matte produced by us is 15.3% Cu, 2.9% Pb, 16.1% Fe and 7% S. It will be noted that this copper-lead ratio of the slag matte itself is better than 5 to 1 and this may be shipped to the copper plant, with the result of eliminating the usual circulating load of copper in the lead blast furnace.

Of no lesser significance is the grade of copper speiss produced. Instead of producing a speiss or matte with a copper to lead ratio of the order of 2 /2 to 1, as has been common in older processes, the speiss produced by the process of the invention may be caused to contain copper to lead in the ratio of the order or 5 to 1 and even much higher. In certain commercial operations practicing the process according to our invention,

speisses have been produced having copper to lead ratios of as high as 16 to 1. Moreover, in practicing the invention, it is not uncommon to produce bullion from the reverberatory containing aslittle as 0.5% Cu.

Inasmuch as the invention provides a smelting process which may be carried out in the reverberatory at a temperature below or not substantially higher than 1000 0., there is a material saving in fuel. And we have found that an operating temperature of about 900 C. is very en'ective. We believe the relatively low temperature at which our process may be practiced accounts in part for the improved and desirable results because the relatively low temperature permits only of lower solubility of lead in the speiss and the flux permits of better liquation and separation of the metallic lead from the speiss. It will be understood, however, that the furnace may be operated, if desired, at higher temperatures and still obtain substantial benefits of the inven- The amount of sodium carbonate, sodium sulphate or other sodium compounds contemplated by the invention, required for the process to function effectively depends to a great extent upon the amount of iron oxid present. We have found that from 2% to 6% of the sodium compounds such as sodium carbonate and sodium sulphate by weight of dross is eflective in treatthant9 1.

' be used, the additional expense is not generally warranted and there is likelihood of producing a slower and more refractor smelting charge. We have found in practicing the invention 1.0% to 1.5% by weight of the dross to'be preferable in obtaining the best results when using our preferred flux.

The amount of litharge to be added to the flux will depend upon the quantity, if any, present in the dross. If substantial quantities are already present it may be unnecessary to add additional litharge as that present will be efiective with the added sodium carbonate or sulphate and,

coke if intimately mixed with the dross charge. Otherwise, the amount of litharge to be added. preferably in the form of litharge slag, produced as mentioned hereinbefore, will range up to about 3.5% by weight of the dross charge. We have found the preferable range to be 2% to 2.5% by weight of the dross when treating drosses generally encountered in commercial operations.

In practicing our invention, we have obtained best results by using fine coke and making certain that the sodium carbonate or the flux-forming sodium compound, coke and litharge slag are intimately mixed with the dross. smelting will proceed at a rapid rate at under 1000 C. provided the slag is removed currently and the furnace kept clear of accumulations of same. We have observed that at least some of the magnetite is held in suspension in the matte; some is in solution and some in chemical combination; and current skimming will remove this iron. The furnace should be skimmed clear particularl before any shut down or delay to smelting operation; otherwise a magnetic oxide crust is apt to segregate in the furnace, which will interfere with smelting rate and'may entail the use of excess fluxing agent and higher temperature to remedy th situation.

In addition to the treatment of, copper-lead dross, our process can be applied advantageously to the treatment of copper-leady mattes having a poor copP I-lead ratio. We have treated matte assaying: 43% Cu, 22% Pb, S, 12% Fe with sodium carbonate, coke, litharge flux and removed or thrown out in the reverberatory 75% of the lead content as metallic lead by proper adjustment of the sodium carbonate, coke, litharge, flux and at the same time producing a copper speiss having a copper to lead ratio of better 7 These desirable results can be obtained eithenby -treating the leady matte separately or by incorporating it in the same "furnace.

with the copper-lead dross. However, in the treatment of copper-leady matte containing particularly high amounts of iron and sulphur we have in some instances had to increase the amount of sodium carbonate in the flux to ten per cent by weight of the matte treated.

It will be seen from the foregoing that'our invention provides a process for smelting copperlead drosses, copper-leady mattes, and the like which can be worked at comparatively low tem-' peratures or, if desired, higher temperatures may be employed. According to the invention, a copper speiss of relatively higher copper to lead ratio and a soda matte in which the copper to lead ratio is also relatively high may be produced. Moreover, bullion containing comparatively little copper may be obtained.

The terms and expressions which have been employed in the foregoing are used as terms of description and it will be understood that in the use of such terms and expressions and in practic ing the invention equivalents are possible and are to be included within the scope of the invention claimed.

What is claimed is:

1. A process of smelting copper-lead dross and the like containing substantial quantities of copper and lead which comprises treating a charge of such material in a reverberatory furnace in the presence of a sodium sulphide matte forming compound, litharge and a carbonaceous reducing agent in controlled proportions and at a temperature to produce a layer of lead bullion, a layer of copper speiss having a copper to lead ratio at least 2.5 to 1 and a layer of sodium sulphide m'atte.

2. Process of smelting copper-lead dross and the like containing substantial quantities of copper and lead which comprises treating the charge in a reverberatory furnace in the presence of a sodium salt containing sulphur and capable of forming a sodium sulphide matte, litharge and a carbonaceous reducing agent in suflicient amounts and at a temperature to cause a sodium sulphide matte and a speiss to be formed in which speiss the copper to lead ratio is better sufiicient amounts and at a temperature to cause a sodium sulphide matte and a speiss to be formed in which speiss the copper to lead ratio is better than 2.5 to 1. I

4. Process of smelting copper-lead dross and the like containing substantial quantities of copper and lead which comprises treating the charge in a reverberatory furnace in the presence of sodium sulphate, litharge, and a carbonaceousjeducing agent in sufficient amounts and at a reducing agent at a temperature to produce a sodium sulphide matte, a copper speiss and lead bullionfsaid percentages being by weight based upon the weight of dross being smelted.

6..Process of treating copper-lead dross containing from 18% to 30% copper, to

lead and smaller amounts of iron which comprises smelting the drossin a reverberatory furnace in the presence of a flux comprising 2%- to 6% sodium sulphate .by weightrof dross charged, litharge and 0.75% to 5% of coke by weight of dross charged, at a temperature to cause a sodium sulphide matte, speiss and bullion to be produced, which matte shall collect substantially all of the iron of the dross, and which speiss shall have a copper to lead ratio of better than 2.5 to l.

7. Process of treating copper-lead dross containing 18% to 30% copper, 50% to 65% lead and smaller amounts of iron which comprises smelting the dross in a reverberatory furnace in the presence of a flux comprising 2% to 6% of sodium sulphate by weight of dross charged, litharge, and 0.75% to5.0% of coke by weight of dross charged at a temperature not exceeding the neighborhood of 1000 C. to cause a sodium sulphide matte, a speiss and bullion to be produced, which slag shall collect substantially all the iron in the dross, which speiss shall have a copper to lead ratio of at least to 1 and which Bullion shall contain less than 1% copper.

8. A process of treating a copper-leady matte having a copper to lead ratio of no greater than 3 to 1 copper to lead to remove lead therefrom and to improve the copper to lead ratio which comprises smelting said matte in a reverberatory furnace in the presence of a flux comprising sodium sulphate, coke and litharge in controlled and suflicient amounts and at a temperature to smelt the charge whereby to produce a copper speiss having a copper to lead ratio of at least 5 to 1 and a bullion containing less than 1% copper.

9. A process of treating a dross, matte or the like, containing substantial quantities of copper, lead and anappreciable quantity of iron, to separate lead therefrom which comprises smelting the charge in a reverberatory furnace in the presence of a flux of sodium sulphate, coke and litharge to produce a sodium sulphate matte which collects substantially all of the iron in the charge and to produce a speiss in which liquation and separation of metallic lead therefrom is facilitated while maintaining the furnace at a smelting temperature at which th solubility of lead in the speiss and copper in the bullion is low.

10. A metallurgical process which comprises intimately intermixing a dross containing 18%-to 30% copper, 50% to 65% lead and smaller amounts of arsenic, antimony, sulphur and iron with from 2% to 6% of sodium sulphate based upon the weight of dross, from .75% to 5.0% of coke based upon the weight of charge, and small amounts of litharge up to 3.5% based upon the weight of dross, whereby to prepare a smeltable charge, smelting said charge in a reverberatory furnace at smelting temperature thereby to form a layer of sodium sulphate matte which collects substantially all the iron in the charge, a layer of copper speiss having a copper to lead ratio at least 5 to 1 and a layer of lead bullion.

11. A metallurgical process which comprises intimately intermixing a dross containing from 18% to 30% copper, to lead and smaller amounts of arsenic, sulphur, and iron with from 3% to 6% sodium sulphate, a small amount of coke and a small amount of litharge whereby to prepare a smeltable charge, smelting said charge in a reverberatory furnace while maintaining the temperature of the furnace at a temperature not substantially higher than 1000 C. thereby to form a matte which collects substantially all the iron in the charge being smelted together with some copper and lead in a ratio at least 5 to 1 of copper to lead, a copper speiss having a copper to lead ratio at least 5 to l and a lead bullion.

12. A metallurgical process which comprises intimately intermixing a dross containing from 18% to 30% copper, 50% to 65% lead and smaller amounts of resenic, antimony, sulphur and iron with about 6% sodium sulphate, a small amount of coke up to about 3%, a small amount of litharge up to about 3% based upon the weight of dross whereby to prepare a smeltable charge,

' smelting said charge in a reverberatory furnace while maintaining the operating temperature of the furnace below 1000 C. thereby to form a matte which collects substantially all the iron in the charge being smelted together with some copper and lead in a ratio at least 5 to l of copper to lead, a copper speiss containing at least 50% copper and some lead in a ratio at least 5 to 1 of copper to lead and a lead bullion containing not substantially more than 1% of copper.

EDWARD P. FLEMING. DONALD H. MCINTOSH. 

